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WO1992002491A1 - Nouveaux derives de (chlorure d'hydroximidoyl)-bis utilises comme fongicides agricoles - Google Patents

Nouveaux derives de (chlorure d'hydroximidoyl)-bis utilises comme fongicides agricoles Download PDF

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Publication number
WO1992002491A1
WO1992002491A1 PCT/US1991/005579 US9105579W WO9202491A1 WO 1992002491 A1 WO1992002491 A1 WO 1992002491A1 US 9105579 W US9105579 W US 9105579W WO 9202491 A1 WO9202491 A1 WO 9202491A1
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optionally substituted
methyl
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group
halogen
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Joseph Eugene Drumm, Iii
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/02—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by halogen atoms
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    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/60—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups having oxygen atoms of carbamate groups bound to nitrogen atoms
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    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/44—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups doubly-bound to carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C07C317/38—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atom of at least one amino group being part of any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylaminosulfones
    • C07C317/42—Y being a hetero atom
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D333/70—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 2

Definitions

  • Hubele CH 66-16,259 claims compounds of Formula ii as
  • This invention pertains to compounds of Formula I including all geometric and stereoisomers, agricultural compositions containing them and their use as fungicides
  • a and A 1 are independently O, NH,— CH 2 O— ,— CH 2 CH 2 O— or a direct bond;
  • X and X 1 are independently SO 2 R 6 , Cl or Br;
  • R 1 and R 2 are independently H; C 1 -C 4 alkyl; C 2 -C 4 alkoxyalkyl; or
  • R 1 and R 2 can be taken together along with the nitrogen atom to which they are attached to form an azetidino, pyrrolidino, piperidino, homopiperidino or morpholino group, each optionally substituted with 1-2 methyl;
  • R 3 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 2 -C 4 alkoxyalkyl;
  • R 4 is C 1 -C 4 alkyl; C 1 -C 4 haloalkyl; C 2 -C 4 alkoxyalkyl; or phenyl optionally substituted with 1-2 substituents selected from the group consisting of halogen, methyl, methoxy, cyano and nitro;
  • R 5 is C 1 -C 4 alkyl; C 1 -C 4 haloalkyl; C 2 -C 4 alkoxyalkyl; or phenyl optionally substituted with 1-2 substituents selected from the group consisting of halogen, methyl, methoxy, cyano and nitro;
  • R 6 is C 1 -C 6 alkyl; C 1 -C 6 haloalkyl; C 2 -C 6 alkoxyalkyl; or phenyl or benzyl, said phenyl or benzyl groups being optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen
  • Q is C 1 -C 6 alkylenyl optionally substituted with 1-2 methyl; C 2 -C 6 alkenylenyl; C 2 -C 6 alkynylenyl; phenylenyl optionally substituted with R 7 ; naphthalenyl optionally substituted with R 7 ; C 3 -C 6 cycloalkylenyl optionally substituted with 1-2 methyl; 1-methylpyrrolyl optionally substituted with R 9 ;
  • heteroaromatic or fused heteroaromatic rings being optionally substituted with R 9 ; NH; or
  • R 7 is 1-4 substitutions selected from the group consisting of halogen, methyl, methoxy, cyano and nitro;
  • R 8 is H, halogen, methyl or methoxy
  • R 9 is selected from 1-2 halogen, cyano, methyl or methoxy
  • R 10 is H or C 1 -C 4 alkyl
  • n 0, 1 or 2;
  • heteroaromatic rings include pyridine, pyrimidine, pyridazine, pyrazine, furan, thiophene, pyrrole, 1-methylpyrrole, pyrazole, 1-methylpyrazole, 1-methyl-1,2,3-triazole, 1-methyl-1,2,4-triazole, oxazole, isoxazole, and thiazole.
  • fused heteroaromatic rings include quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, indole, 1-methylindole, benzimidazole,
  • alkyl used either alone or in compound words such as “haloalkyl” denotes straight chain or branched alkyl, especially methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl, hexyl, heptyl or octyl isomers.
  • alkynylene particularly include CsC and
  • Cycloalkylenyl particularly includes cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene.
  • halogen either alone or in compound words such as “haloalkyl”, denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” particularly include F 3 C, CICH 2 ,
  • the total number of carbon atoms in a substituent group is
  • C i -C j prefix where i and j are numbers from 1 to 6.
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates CH 3 OCH 2 CH 2 and CH 3 CH 2 OCH 2 .
  • alkoxyalkyl include CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • a and A 1 are independently NH,— CH 2 O— , or a direct bond
  • Q is C 1 -C 6 alkylenyl optionally substituted with 1-2 methyl
  • a and A 1 are the same;
  • X and X 1 are both SO 2 R 6 or Cl;
  • Q is C 1 -C 6 alkylenyl optionally substituted with 1-2 methyl
  • C 2 -C 6 alkenylenyl; C 2 -C 6 alkynylenyl; or Q is selected from the group of
  • R 6 is phenyl optionally substituted with methyl, trifluoromethyl, methoxy, cyano, nitro or 1-3 halogen.
  • a and A 1 are both NH or a direct bond.
  • Q is selected from the group consisting of:
  • the compounds of Formulae I-III can be prepared from compounds of Formulae IV and/or V and an appropriate electrophilic reagent of Formula VI in an inert solvent with a base used either as a catalyst or acid scavenger.
  • Suitable solvents include polar aprotic solvents such as acetonitrile or dimethylformamide; ethers such as tetrahydrofuran, dimethoxyethane or diethyl ether; ketones such as acetone or 2-butanone; hydrocarbons such as toluene or benzene; or halogenated hydrocarbons such as dichloromethane, chloroform, or carbon tetrachloride.
  • Appropriate bases include alkali metal alkoxides, such as sodium methoxide or potassium tert-butoxide, inorganic bases such as sodium hydride or potassium carbonate, or tertiary amine bases such as triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or 1,4-diazabicyclo[2.2.2]octane (DABCO).
  • the reaction temperature can vary between 0°C and 150°C for periods of 1 to 96 hours, depending on the choice of base, solvent, temperature, and substrates.
  • substituted hydroximidoyl chlorides or bromides of Formula I can be prepared from the corresponding aldoximes of Formulae VII and VIII with halogens (H. Metzger, strigos).
  • Compounds of Formula II can be made by an alternate synthetic scheme.
  • Compound X can be made following a procedure given by L. Grehn, K Gunnarsson and U. Ragnarsson, Acta Chem. Scand. B, 1987, 41:18.
  • a novel method of preparation of compounds of Formulae II and III comprises sequential preparation of the novel chloroformate XI by reaction of compounds of Formulae IV and V with phosgene in the presence of organic bases such as N,N-diethylaniline and pyridine.
  • R' can represent any appropriate embodiment of the above defined Q groups.
  • Phosgene substitutes may also be used (e.g., diphosgene, triphosgene) according to the literature of H. Eckert, B. Forster, Angew. Chem, Int. Ed., Eng., 1987, 26:894; and K Kumita, Y. Iwakura, Org. Synth., 1980, 59:195.
  • n may be independently 0 or 1.
  • the bridging groups, Q which are not commercially available, may be prepared by one skilled in the art following methods described in the following comprehensive organic chemistry tests:
  • thiocarboxamide and thioketone compounds shown below can be prepared from the carboxamide or ester compounds, respectively, by methods described elsewhere (see S. Scheibye, E. S. Pedersen and
  • Compounds of Formulae IV and V can also be prepared by conversion of other compounds of Formulae IV and V by standard methods of organic reactions, recognizable by those skilled in the art, such as, but not limited to, reduction and oxidation.
  • the ⁇ -chloroaldoximes of Formulae IV and V can be prepared by treating amines of Formula XIX with sodium nitrite and hydrochloric acid (see G. S. Skinner, J. Am Chem Soc.. 1924, 46:731).
  • the ⁇ -chloroaldoximes of Formulae IV and V can also be prepared from aldoximes of Formula XX by treatment with N-chlorosuccinimide (see K E. Larsen and K B. G. Torsell, Tetrahedron. 1984, 40:2985) or t-butylhypochlorite (see C. J. Peake and J. H. Strickland, Synth. Comm., 1986.16:763).
  • Some ⁇ -haloaldoximes of Formulae IV and V may be prepared from amide oximes XXI by treatment with sodium nitrite in hydrohalic acid solution (see M. Kocevar, S. Polanc, M. Sollner, M. Tisler and B. Vercek, Synth. Comm., 1988,18:1427).
  • ⁇ -haloaldoximes of Formulae IV and V can be prepared from trihalomethyl compounds of Formula XXII by basic hydrolysis in the presence of hydroxylamine (see A P. Kozikowski and M. Adamczyk, J. Org. Chem., 1983, 48:366).
  • the ⁇ -haloaldoximes of Formulae IV and V can be prepared by the reaction of nitrile N-oxides of Formula XXIII with hydrohalic acids (see C. Grundmann, V. Mini, J. M. Dean, and H. -D. Frommeld, Justis Liebigs Ann. Chem., 1965, 687:191).
  • nitrile N-oxides of Formula XXIV can be prepared by several methods well known in the chemical art (for a summary of methods, see T. Shimizu, Y. Hayashi, and K Taramura, Bull. Soc. Chem. Jpn.. 1984, 57:2531). The most familiar method involves treating an
  • ⁇ -chloroaldoxime of Formula Va with an inorganic base such as sodium hydroxide or sodium carbonate or an organic base such as triethylamine followed by trapping the nitrile N-oxide of Formula XXIV with a hydrohalic acid.
  • an inorganic base such as sodium hydroxide or sodium carbonate or an organic base such as triethylamine
  • a new ⁇ -haloaldoxime of Formula V is produced.
  • the carboxamide and carboxylic acid ester compounds of Formula V can be prepared by the procedures taught in the U.S. Patents
  • the cyano compound of Formula V can be prepared by methods already reported (see A. P. Kozikowski and M. Adamczyk, J. Org. Chem., 1983, 48:366).
  • the ketone compounds of Formula V can be prepared from halomethyl ketones of Formula XXV by treatment with an alkyl nitrite and hydrochloric acid (see N. Levin and W. H. Hartung, Org. Synthesis. 1944, 24:25).
  • the ketone compounds of Formula V can also be prepared from halomethyl ketones of Formula XXV by treatment with dimethyl sulfide to afford compounds of Formula XXVI, which are then treated with sodium nitrite and hydrochloric acid (see Y. Ofsuji, Y. Tsuju, A Yoshida and E. Imoto, Bull Chem Soc. Japan. 1971, 44:223).
  • the ketone compounds of Formulae IV and V can be prepared from ⁇ -ketosulfoxides of Formula XXVII by treatment with sodium nitrite in hydrohalic acid solution (see Y. Otsuji, Y. Tsujii, A Yoshida and E. Imoto, Bull. Chem Soc. Japan. 1971, 44:219).
  • the ketone compounds of Formulae IV and V can also be prepared from compo ⁇ mds of Formula XX by treatment with chlorine gas (see
  • the thioalkyl and thioaryl compounds of Formulae IV and V can be prepared from dihaloformaldoxime XXVIII (see D. Chiarino,
  • Formulae IV and V can be prepared from ⁇ -diazosulfones of Formula XXX and nitrosyl chloride (see J. C. Jagt, I. van Buuren, J. Strating and A M. Van Leusen, Synth. Commun., 1974, 4:311). *
  • the compounds of this invention will generally be used in formulation with a liquid or solid diluent or with an organic solvent.
  • Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation.
  • formulations broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to 20% surfactant(s) and b) about 5% to 99% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
  • compositions Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
  • Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, “Solvents Guide,” 2nd Ed.,
  • Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill.
  • Water dispersible granules may be produced by agglomerating a fine powder composition (see, for example, B. Cross and H. Scher, "Pesticide Formulations", ACS Symposium Series 371,
  • Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084).
  • Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering. December 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's
  • the ingredients are blended and ground in a hammermill to produce a high strength concentrate essentially all passing a U.S.S. No. 50 Sieve (0.3 mm openings). This material may then be formulated in a variety of ways.
  • the ingredients are combined and stirred to produce a solution, which can be used for low volume applications.
  • the compounds of this invention are useful as plant disease control agents. They provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete. Ascomycete. and Oomycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include, Plasmopara viticola. Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septorianodorum, Cercosporidium personatum, Cercospora arachidicola,
  • Pseudocercosporella herpotrichoides Cercospora beticola, Botrytis cinerea. Monilinia fructicola, Pyricularia oryzae, Podosphaera leucotricha, Venturia inaequalis, Puccinia recondita, Puccinia gramminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, and other species closely related to these
  • the compounds of this invention can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides or other biologically active compounds in order to achieve desired results with a minimum of expenditure of time, effort and material.
  • Suitable agents of this type are well-known to those skilled in the art. Some are listed below: Fungicides
  • O-ethyl-S,S-diphenylphosphorodithioate edifenphos
  • Disease control is ordinarily accomplished by applying an effective amount of the compound, pre-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs.
  • the compound may also be applied to the seed, to protect the seed and seedling.
  • Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 10 g/ha to 10,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed.
  • test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on apple seedlings. The following day the seedlings were inoculated with a spore suspension of Venturia inaequalis (the causal agent of apple scab) and incubated in a saturated atmosphere at 20°C for 24 hr, and then moved to a growth chamber at 22°C for 11 days, after which disease ratings were made.
  • a spore suspension of Venturia inaequalis the causal agent of apple scab
  • test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on peanut seedlings. The following day the seedlings were inoculated with a spore suspension of Cercosporidium personatum (the causal agent of peanut late leafspot) and incubated in a saturated atmosphere at 22°C for 24 hr, a high humidity atmosphere at 22°C to 30°C for 5 days, and then moved to a growth chamber at 29°C for 6 days, after which disease ratings were made.
  • a spore suspension of Cercosporidium personatum the causal agent of peanut late leafspot
  • test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 hr, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.
  • Puccinia recondita the causal agent of wheat leaf rust
  • test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on rice seedlings. The following day the seedlings were inoculated with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27°C for 24 hr, and then moved to a growth chamber at 30 C for 5 days, after which disease ratings were made.
  • Trem 014 polyhydric alcohol esters
  • test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestams (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20°C for 24 hr, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
  • Phytophthora infestams the causal agent of potato and tomato late blight
  • test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on grape seedlings. The following day the seedlings were inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20°C for 24 hr, moved to a growth chamber at 20°C for 6 days, and then incubated in a saturated atmosphere at 20°C for 24 hr, after which disease ratings were made.
  • Plasmopara viticola the causal agent of grape downy mildew
  • test compounds were dissolved in acetone in an amount equal to 3 % of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20°C for 48 hr, and moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
  • Botrytis cinerea the causal agent of gray mold on many crops
  • Results for Examples A to G are given in Table A.
  • a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the carrier sprayed controls).
  • NT indicates that no test was performed.
  • CMPD complementary metal-oxide-semiconductor

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Abstract

Des composés à action antifongique de la formule (I) sont décrits.
PCT/US1991/005579 1990-08-06 1991-08-06 Nouveaux derives de (chlorure d'hydroximidoyl)-bis utilises comme fongicides agricoles Ceased WO1992002491A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625987A (en) * 1966-11-10 1971-12-07 Ciba Ltd Cyano carbamoyloximes
US3819700A (en) * 1970-04-23 1974-06-25 R Bellina 2-(hydrocarbylthio)-2-(hydroxyimino)-acetamide s-oxides and derivatives
US3954992A (en) * 1973-07-02 1976-05-04 E. I. Du Pont De Nemours And Company 2-Cyano-2-hydroxyiminoacetamides as plant disease control agents
EP0008474A2 (fr) * 1978-08-24 1980-03-05 Shell Internationale Researchmaatschappij B.V. Compositions pesticides contenant un sulfure d'acide carbamique et un insecticide pyréthroide synthétique et leur utilisation
EP0015745A1 (fr) * 1979-03-06 1980-09-17 E.I. Du Pont De Nemours And Company Sulfures de carbamoyle à activité pesticide, leur préparation et leur utilisation
US4475945A (en) * 1980-01-14 1984-10-09 Ciba-Geigy Corporation Aminoglyoxyloitrile oximino carboxylic acid esters and thio esters for the protection of crops against injury by herbicides
EP0198687A2 (fr) * 1985-04-12 1986-10-22 Rohm And Haas Company Alpha-polyhalocétoximes
WO1986005950A1 (fr) * 1985-04-18 1986-10-23 Union Carbide Corporation Carbamates de bis alkylthio-alkylimino-n-alkyle stabilises thermiquement

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625987A (en) * 1966-11-10 1971-12-07 Ciba Ltd Cyano carbamoyloximes
US3819700A (en) * 1970-04-23 1974-06-25 R Bellina 2-(hydrocarbylthio)-2-(hydroxyimino)-acetamide s-oxides and derivatives
US3954992A (en) * 1973-07-02 1976-05-04 E. I. Du Pont De Nemours And Company 2-Cyano-2-hydroxyiminoacetamides as plant disease control agents
EP0008474A2 (fr) * 1978-08-24 1980-03-05 Shell Internationale Researchmaatschappij B.V. Compositions pesticides contenant un sulfure d'acide carbamique et un insecticide pyréthroide synthétique et leur utilisation
EP0015745A1 (fr) * 1979-03-06 1980-09-17 E.I. Du Pont De Nemours And Company Sulfures de carbamoyle à activité pesticide, leur préparation et leur utilisation
US4475945A (en) * 1980-01-14 1984-10-09 Ciba-Geigy Corporation Aminoglyoxyloitrile oximino carboxylic acid esters and thio esters for the protection of crops against injury by herbicides
EP0198687A2 (fr) * 1985-04-12 1986-10-22 Rohm And Haas Company Alpha-polyhalocétoximes
WO1986005950A1 (fr) * 1985-04-18 1986-10-23 Union Carbide Corporation Carbamates de bis alkylthio-alkylimino-n-alkyle stabilises thermiquement

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IL99078A0 (en) 1992-07-15
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